WO2001002088A1 - Procede de commande du processus de fabrication des polyols - Google Patents
Procede de commande du processus de fabrication des polyols Download PDFInfo
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- WO2001002088A1 WO2001002088A1 PCT/FI2000/000610 FI0000610W WO0102088A1 WO 2001002088 A1 WO2001002088 A1 WO 2001002088A1 FI 0000610 W FI0000610 W FI 0000610W WO 0102088 A1 WO0102088 A1 WO 0102088A1
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- WIPO (PCT)
- Prior art keywords
- infrared
- calibration
- stream
- aldehyde
- analysis
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 211
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229920005862 polyol Polymers 0.000 title description 17
- 150000003077 polyols Chemical class 0.000 title description 17
- 230000008569 process Effects 0.000 claims abstract description 132
- 239000000203 mixture Substances 0.000 claims abstract description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000012544 monitoring process Methods 0.000 claims abstract description 23
- 238000004566 IR spectroscopy Methods 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 25
- 230000003287 optical effect Effects 0.000 claims description 21
- 150000001299 aldehydes Chemical class 0.000 claims description 18
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 16
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 15
- 239000012467 final product Substances 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004886 process control Methods 0.000 claims description 5
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002349 favourable effect Effects 0.000 claims description 4
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 238000002329 infrared spectrum Methods 0.000 claims description 3
- 238000007619 statistical method Methods 0.000 claims description 3
- 239000001893 (2R)-2-methylbutanal Substances 0.000 claims description 2
- ZHDDGKNACKSKEF-UHFFFAOYSA-N 2,3-diphenylpropanal Chemical compound C=1C=CC=CC=1C(C=O)CC1=CC=CC=C1 ZHDDGKNACKSKEF-UHFFFAOYSA-N 0.000 claims description 2
- UQURIQWAEZGLAC-UHFFFAOYSA-N 2-cyclohexylpropanal Chemical compound O=CC(C)C1CCCCC1 UQURIQWAEZGLAC-UHFFFAOYSA-N 0.000 claims description 2
- SHGPBDQRELYPLO-UHFFFAOYSA-N 2-ethyl-3-methylbutanal Chemical compound CCC(C=O)C(C)C SHGPBDQRELYPLO-UHFFFAOYSA-N 0.000 claims description 2
- OZGRFPZYTKHWMZ-UHFFFAOYSA-N 2-ethylpentanal Chemical compound CCCC(CC)C=O OZGRFPZYTKHWMZ-UHFFFAOYSA-N 0.000 claims description 2
- DIBSCKQIZZVKMG-UHFFFAOYSA-N 2-phenylbutanal Chemical compound CCC(C=O)C1=CC=CC=C1 DIBSCKQIZZVKMG-UHFFFAOYSA-N 0.000 claims description 2
- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 claims description 2
- VELDYOPRLMJFIK-UHFFFAOYSA-N cyclopentanecarbaldehyde Chemical compound O=CC1CCCC1 VELDYOPRLMJFIK-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000013178 mathematical model Methods 0.000 claims 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims 1
- 125000001145 hydrido group Chemical group *[H] 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000005070 sampling Methods 0.000 description 13
- 238000004497 NIR spectroscopy Methods 0.000 description 12
- 238000002790 cross-validation Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- -1 acryl Chemical group 0.000 description 2
- 238000011021 bench scale process Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012067 mathematical method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001159 Fisher's combined probability test Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007620 mathematical function Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
- B01J2219/00193—Sensing a parameter
- B01J2219/00195—Sensing a parameter of the reaction system
- B01J2219/002—Sensing a parameter of the reaction system inside the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
- B01J2219/00211—Control algorithm comparing a sensed parameter with a pre-set value
- B01J2219/00213—Fixed parameter value
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
- B01J2219/00222—Control algorithm taking actions
- B01J2219/00227—Control algorithm taking actions modifying the operating conditions
- B01J2219/00229—Control algorithm taking actions modifying the operating conditions of the reaction system
- B01J2219/00231—Control algorithm taking actions modifying the operating conditions of the reaction system at the reactor inlet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
- B01J2219/00222—Control algorithm taking actions
- B01J2219/00227—Control algorithm taking actions modifying the operating conditions
- B01J2219/0024—Control algorithm taking actions modifying the operating conditions other than of the reactor or heat exchange system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a method for monitoring and controlling the manufacturing process of polyhydroxy alcohols, or polyols. More specifically, the invention is directed to a process for producing polyols from formaldehyde and another aldehyde by aldolization and hydrogenation, and to the monitoring and control thereof by means of infrared spectroscopy. In this method, the production of polyols is controlled by analyzing the composition of one or several process streams with infrared spectroscopy, and by using the difference between the predicted concentration and the desired concentration of a substance to control the process. In addition, the invention relates to a method for producing polyols, the method being monitored and controlled with infrared spectroscopy.
- Polyhydroxy alcohols such as neopentyl glycol are important intermediates in the production of synthetic resins, including acryl resins, polyester resins, polyuretane resins, alkyd resins, and polycarbonate resins. Polyols are also used in the production of plasticizers, synthetic lubricants, surface active agents and the like. As is known, the aldolization reaction between formaldehyde and another aldehyde may be carried out continuously in the presence of a catalyst.
- neopentyl glycol is obtained by reacting formaldehyde with isobutyric aldehyde in the presence of an amine resulting in hydroxypivalic aldehyde as the main product that is further hydrogenated, giving the desired neopentyl glycol as the final product.
- This neopentyl glycol may be further purified for instance by distillation.
- the process for producing polyols generally comprises three steps, that is, the aldolization step, the hydrogenation step, and the separation step. Each process step may comprise several units, arranged for instance in series.
- the compositions of the starting materials, solvents, aldolization product, by-products, and the final product in different process streams are monitored by taking samples from different points of the process several times a day. Such frequent sampling is necessary, since the operation of the aldolization reaction typically changes with time. For instance, if an ion exchange resin is used as a catalyst, the operation of the reactor is changed by the deactivation of the catalyst. Organic compounds in the sample are analyzed with gas chromatography (GC), or high pressure liquid chromatography (HPLC). Water determinations are carried out with Karl Fischer titration. All these analytical methods are time consuming, require several instruments, and occupy laboratory personnel.
- GC gas chromatography
- HPLC high pressure liquid chromatography
- the patent US 5 349 188 discloses a continuous analysis of hydrocarbon mixtures with a near infrared spectroscopic method in the production of fuel mixtures.
- the patent US 5 712 481 presents a method based on near infrared spectroscopy for the determination of aromatic hydrocarbons as well such as benzene, toluene, xylene and alkyl benzenes in applications of the petroleum industry such as in catalytic cracking, alkylation, and isomerization, as well as in the production of fuel mixtures.
- Near infrared spectroscopic methods for monitoring and controlling a process in the production of polyesters are disclosed in publications EP 0 839 848 and WO 96/10009.
- the publication WO 98/29787 discloses the monitoring and controlling of the process for producing halogenated butyl rubber, and a method for controlling the properties of the product by means of a continuous, real-time analyzer system comprising a near infrared spectrometer and a viscosimeter.
- the publication EP 0 801 299 presents a method for controlling of a process wherein the absorption is measured with a near infrared spectroscopic method using a wavelength varying between 600 and 2600 nm. The signals of said absorptions or mathematical functions thereof are compared with the corresponding values of standard samples.
- NIR near infrared spectroscopy
- the object of the present invention is to provide a method for controlling the production process of polyols, and a process for producing polyols.
- the process for producing polyols may be controlled in almost real time with a process monitoring and/or controlling system based on infrared spectroscopy.
- the compositions of the starting materials, solvents, intermediates, impurities, by-products, and the final product may be monitored almost simultaneously at different process points of the process streams.
- formaldehyde and another aldehyde are reacted in the presence of a suitable catalyst, preferably an amine catalyst such as a basic anion exchange resin, to form an aldolization product.
- a suitable catalyst preferably an amine catalyst such as a basic anion exchange resin
- the other aldehyde may be selected from the group consisting of ethanal, propanal, butanal, 2-methylpropanal (isobutyric aldehyde), 2-methylbutanal, 2-ethylpentanal, 2-ethylhexanal, 2-isopropylbutanal, 2-phenylpropanal, 2-cyclohexylpropanal.
- the characteristic feature of the process is that the catalyst is deactivated by the acids in the process stream.
- the aldolization catalyst is regenerated once in 2 - 10 days.
- the properties of the aldolization product may be influenced by adjusting the process conditions, such as feed rates of the starting material, temperatures of the reactors, flow rates and the timing of the regeneration of the catalyst. For the optimal control of the process, it is very useful to know the composition of the aldolization product in different reactors in real time.
- the process conditions may be adjusted in such a manner that the composition of the aldolization product will remain as desired.
- the process conditions must be continuously adjusted during the run, since the acitivity of the catalyst declines constantly until a state is attained wherein the catalyst should be regenerated to restore the original level of its activity.
- a catalyst suitable for the process is used.
- the hydrogenation is preferably carried out at an elevated temperature and pressure.
- the separation step after the hydrogenation the desired alcohol is separated from the reaction mixture with a suitable method, for instance by distillation.
- the solvents may be recycled back to the hydrogenation or aldolization step, if necessary.
- absorbance measurements from process streams are carried out with an infrared spectrophotometer based on reflectance method or flow-through method or a combination thereof.
- an optical cell or another measuring head which is placed directly in the process stream or to a separate analyzer line carrying a stream from the process stream.
- the optical cell or the measuring head is preferably connected to the spectrophotometer with fibre optical cables, or it may be connected directly to the infrared spectrophotometer.
- Several optical cells or measuring heads may be connected to a single spectrophotometer with fibre optical cables through a multiplexer, allowing the compositions of different process streams to be monitored alternately.
- Figure 1 shows the principle of a process wherein several sample points are monitored with a single infrared spectrophotometer.
- This figure shows a block diagram of the principle of the process for the preparation of alcohols wherein the starting materials are fed to the aldolization step and the final product is recovered from a separation step.
- This process comprises several measuring cells for monitoring the composition of the process stream in different steps. The measuring cells are connected to a spectrophotometer with optical fibres through a multiplexer that alternately transmits a signal from each of the cells to the spectrophotometer. Alternatively, each cell has its own spectrophotometer.
- the spectrophotometer measures the absorbance spectrum of the process stream, and then, on the basis of this spectrum, a computer determines the composition of the process stream according to a previously programmed calibration model. The difference between the measured, and the desired compositions of the process stream is used for the control of the process manually, or this information is entered to a process computer controlling the temperatures, flow rates and the timing of the regeneration of the aldolization catalyst on the basis of this information.
- the optical cell or measuring head is used for irradiation of the process stream with mid infrared or near infrared radiation having a wavelength between 800 and 5000 run. Using this measuring head, the absorbance spectrum of at least one process stream is measured in this mid infrared and/or near infrared region of 800 - 5000 nm.
- the absorbance of the reaction mixture is measured several times during the process with one or more measurements by using a single wavelength or several different wavelengths selected from this mid infrared and/or near infrared region.
- the wavelengths used are selected with statistical methods to obtain the most favorable correlation ratio between known and measured analysis results in calibration.
- a suitable multivariant method is used to collect the necessary composition data from the spectrum, since the absorbances of different components overlap in mid and near infrared range. Especially the spectrum of water acting as a solvent partly overlaps the absorption of other components.
- Figure 2 shows the absorption spectra of different components in near infrared range with the equipment settings of Table 1. The absorption spectrum of Figure 2 shows that the spectra of the starting materials, products and solvents are very similar.
- the spectral information is analyzed with mathematical and computational methods to obtain the necessary composition data.
- the mathematical calibration model is determined with calibration samples covering the variation of all the components to be measured found in actual process conditions.
- Infrared spectrophotometry may thus be used to analyze the process stream, and then, with a computer software, the spectrum of the process stream is compared to the background spectrum and the concentrations of the substances of interest in the process stream in question are calculated with a preprogrammed calibration model.
- the measuring head of the infrared spectrophotometer may be connected to the spectrophotometer with optical fibres, or it may be connected directly to the spectrophotometer.
- the spectrophotometer is connected to the controlling computer carrying out the necessary computation of the absorbance spectra and calculation of the concentrations of the substances according to the calibration model.
- This computer may opionally be in direct contact with the system for controlling the process that adjusts the temperatures and flow rates of the process, and controls the regeneration of the catalyst.
- the analysis data from the computer may also be used to control the process manually.
- the correctness of the calibration model created may be determined with cross validation or a separate test group. In cross validation, one or several samples are omitted from the calibration group, the calibration model is created with the remaining samples and then, the correctness of the model is tested for the samples omitted from the calibration group.
- the analytical method based on infrared spectroscopy used for controlling the production of polyhydroxy alcohols is accompanied with significant advantages over methods of the prior art.
- the invention makes a continuous monitoring of a process possible in almost real time, the analysis delay being only about one minute. Moreover, it allows a process to be controlled continuously by using the difference between the composition measured with infrared spectrophotometer and the desired composition to control the process according to Figure 1.
- the method of the invention neither requires highly skilled personnel nor is it laborious in comparison with traditional analysis methods.
- the analysis is carried out directly from the process stream and thus, no sampling from the process is needed. Due to the low energy level of near infrared radiation compared for instance to UV radiation, the analyzer neither affects nor harms the substances being analyzed.
- the physical properties of the sample have no influence on the analysis result, since the absorption spectrum is used for the analysis.
- the process stream may be used as such for the analysis without any preparation. Further, the analysis will not change the process stream, nor produce waste to be disposed. Because of the fact that no removal of samples from the process stream is necessary, there is no occupational safety risk during sampling, and no errors influencing the analysis result due to incorrect sampling or incorrect sample preparation are possible.
- the method of the invention allows an overall economic control of the process for producing polyhydroxy alcohols, and an overall economic production of polyhydroxy alcohols with this process, maintaining the quality of the product constant despite of varying process conditions.
- an on-line control the aldolization and hydrogenation steps are constantly under control and the process is not allowed to drift to an inacceptable state leading to an impure product that would necessitate several distillation steps to separate the by-products. Accordingly, thanks to this on-line control process, a simpler purification unit may be designed, and product obtained is purer and has a better quality.
- the method of the invention is useful in various steps of the production of polyhydroxy alcohols, as also shown by the following examples 1 - 4.
- the method of the invention is particularly preferable in the process for producing polyhydroxy alcohols comprising an aldolization step wherein an ion exchange resin is used as the catalyst.
- the regeneration cycle of the resin catalyst may then be optimized by monitoring the conversion level or the composition of the product.
- the immediate advantages of the invention are the facts that in this analysis method, the analysis delay is shorter and the method of analysis is less laborious when compared with traditional methods of analysis.
- the shorter analysis delay allows a more precise process control and makes possible to connect the analysis method directly to the process control system.
- the versatile NIR method of the invention is by far superior over other methods. All analyses may be carried out simultaneously, quickly and reproducibly and all components of the process may be determined at the same time.
- the following examples illustrate the analytical precision of the method, the working time needed therefor, and the reproducibility thereof. The advantages of the method are also evident from these examples.
- a calibration model based on near infrared spectroscopy was drawn up for the aldolization step of the process for producing neopentyl glycol (NPG).
- NPG neopentyl glycol
- hydroxypivalic aldehyde is obtained by allowing formaldehyde to react with isobutyric aldehyde in the presence of an amine catalyst.
- formalin may be used as the formaldehyde source containing besides formaldehyde water and methanol as solvents.
- the calibration model was drawn up for all main components found in the aldolization step of the NPG production, that is, the aldolization product hydroxypivalic aldehyde, the starting materials isobutyric aldehyde and formaldehyde, and the solvents methanol and water.
- 80 calibration samples were prepared, part of them by mixing pure substances found in the process, and part of them by taking as samples from bench scale aldolization test equipment. These samples were analyzed with gas chromatography and high pressure liquid chromatography to determine the compositions thereof.
- a PLSplus/IQ statistical software based on PLS multivariant method was used. The number of the main components included in the PLS model was selected with cross validation.
- the calibration samples were prepared to cover the whole concentration range found in the aldolization step for all the substances to be calibrated. There was no significant correlation between the concentrations of the substances to be calibrated.
- the correctness of the calibration model was determined with cross validation by using the selected amount of the main component. The calibration results for each of the substances calibrated are shown in Table 2 below.
- the table shows the concentration range used in the calibration, the number of the main components in the calibration model, and the correlation (Q 2 ) of the test group from the cross validation, illustrating the correctness of the calibration with samples not belonging to the calibration model.
- the near infrared spectrophotometer may be calibrated to monitor the composition of the aldolization product in all process conditions found. Accordingly, for instance in a system of reactors in series, the composition of the aldolization product in the starting material feed, in all reactors and in the final aldolization product may be monitored with the analysis method of the invention.
- the calibrated concentration range covers all concentration variations of all substances to be calibrated in this range.
- neopentyl glycol is obtained by allowing hydroxypivalic aldehyde to react with hydrogen in the presence of a catalyst.
- Solvents used in the process are typically water and methanol.
- the separation step the neopentyl glycol obtained from the hydrogenation is purified and the solvents are removed.
- the calibration of the hydrogenation and purification steps was carried out with the specifications shown in Table 1.
- the calibration was carried out in such a way that the calibration samples contained all substances found in the hydrogenation and separation steps. Further, there was no significant correlation between the concentrations of the substances to be calibrated.
- Table 3 shows the substances present in the calibration samples and the concentration ranges thereof in the calibration.
- the concentration ranges used were so wide that in addition to distinct hydrogenation steps, the same calibration model is suitable for several substance streams of the purification step wherein the solvents are separated and recycled to the process and the impurities are removed from the product.
- the calibration was carried out for neopentyl glycol and for the solvents water and methanol found in hydrogenation and separation steps.
- the calibration results are presented in Table 4 showing the concentration range used in calibration, the number of the main components of the calibration model, and the correlation (Q ⁇ ) of the test group from the cross validation, illustrating the functionality of the calibration with samples not belonging to the calibration model. Table 4
- the near infrared spectrophotometer may be calibrated to monitor in the hydrogenation step and in the purification step of the product, the purity of the final product (neopentyl glycol) and the concentrations of the solvents in different process conditions. Accordingly, for instance in a system of reactors in series for hydrogenation, the hydrogenation conversion in all reactors may be monitored with the method of analysis according to the invention, since the total concentration range of the product, that is from 0 to 90 wt-%, may be covered with this calibration model. Due to the wide concentration range,the concentrations of the product and the solvent may also be monitored in several process streams of the purification step.
- a calibration model based on infrared spectroscopy was drawn up for the aldolization step of the process for producing 2-butyl-2-ethyl-l,3-propane diol (BEPD).
- BEPD 2-butyl-2-ethyl-l,3-propane diol
- the BEPD aldol is obtained by reacting formaldehyde with 2-ethylhexanal in the presence of an amine catalyst.
- the calibration model was created for the aldolization product, BEPD aldol, and for the other starting material, the 2-ethylhexanal, and for the hydrogenation product, BEPD being formed in this process in minor amounts already in the aldolization step.
- 50 calibration samples were prepared, part of them by mixing pure substances, and part of them by taking samples from a laboratory process. The samples were analyzed with CG and HPLC methods to determine the compositions thereof. The apparatuses and operating conditions are shown in Table 5.
- the near infrared spectrophotometer may be calibrated to monitor the composition of the aldolization product in the process for producing BEPD.
- TMP trimethylol propane
- aldolization step n-butyric aldehyde and formaldehyde are reacted in the presence of an amine catalyst to form TMP aldol that may further be hydrogenated to TMP.
- formalin may be used as the formaldehyde source containing besides formaldehyde water and methanol as solvents.
- the calibration was carried out by using the apparatuses and settings shown in table 1.
- a PLS multivariant method was used.
- the number of the main components of the PLS model was selected with cross validation.
- the calibration was carried out in such a manner that the calibration samples contained most of the substances pressent in the process, and that there was no significant correlation between the concentrations of the substances to be calibrated.
- the correctness of the calibration model was determined with cross validation by using the selected amount of the main component.
- Table 7 shows the concentration range used in the calibration, the number of the main components in the calibration model, and the correlation (Q 2 ) of the test group from the cross validation, O 01/02088
- the near infrared spectrophotometer may be calibrated to monitor the process for producing TMP.
- the method of analysis according to the invention based on infrared spectro- photometry, and the chromatographic (GC and HPLC) analysis methods used traditionally in the production of polyhydroxy alcohols were compared in the aldolization step of the bench scale process for producing neopentyl glycol.
- the method of the invention was used to analyze hydroxypivalic aldehyde, isobutyric aldehyde, formaldehyde and methanol in the aldolization mixture.
- the apparatuses and operation conditions, and the calibration model were the same as in Example 1.
- the aldolization process equipment comprised three reactors in series.
- the catalyst used in the process was an anion exchange resin.
- a flow-through cell was connected to an infrared spectrophotometer with fibre optical cables. The cell was joined to the exits of the three reactors in such a manner that the flow could be directed to the cell alternately from any of the three reactors with the analyzer pump.
- the method of the invention and the traditional gas chromatographic and high pressure chromatographic analysis methods were compared for five days by monitoring the compositions of the effluents of the reactors. With the near infrared spectroscopic method of the invention, the process stream was continuously monitored by alternately analysing each sampling point.
- the work load needed to carry out the analyses, and the analysis delay between the sampling and the results were determined.
- the work load consists of the running of the monitoring samples and adjustments of the apparatuses.
- the work load and the analysis delay in the chromatographic methods are caused by the sampling, sample preparation and the running of the chromatogram.
- the results shown in Table 9 are calculated for a single sample at a time. The sample delay increases significantly if samples from all the reactors are determined simultaneously with traditional methods.
- the infrared spectrophotometric analysis method of the invention and the chromatographic analysis methods (GC and HPLC) used traditionally for the monitoring of the production of polyhydroxy alcohols were compared for the monitoring of the production of hydroxypivalic aldehyde.
- the reproducibility of said methods in continuous process monitoring was compared by pumping hydroxypivalic aldehyde mixture through a transmission flow-through cell connected with fibre optical cables to an infrared spectrophotometer. A sampling point for taking samples for chromatography was situated immediately after the flow-through cell.
- the concentration of hydroxypivalic aldehyde was determined 25 times from a mixture containing about 45 wt-%, HP A, with a gas chromatographic method (GC), a high pressure chromatographic method (HPLC), and with the method of the invention (NIR).
- GC gas chromatographic method
- HPLC high pressure chromatographic method
- NIR method of the invention
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Abstract
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AU58318/00A AU5831800A (en) | 1999-07-06 | 2000-07-04 | Method for the control of the manufacturing process of polyols |
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FI991542A FI991542A (fi) | 1999-07-06 | 1999-07-06 | Menetelmä moniarvoisten alkoholien valmistusprosessin ohjaamiseksi |
FI991542 | 1999-07-06 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102023140A (zh) * | 2011-01-07 | 2011-04-20 | 安徽中烟工业公司 | Nir技术测定1-2丙二醇含量方法 |
US8174503B2 (en) | 2008-05-17 | 2012-05-08 | David H. Cain | Touch-based authentication of a mobile device through user generated pattern creation |
EP2920137A4 (fr) * | 2012-11-13 | 2016-06-15 | Lyondell Chemical Tech Lp | Régulation d'un procédé par spectroscopie raman |
EP2895689A4 (fr) * | 2012-09-14 | 2016-10-05 | Halliburton Energy Services Inc | Systèmes et procédés pour contrôler des processus de séparation pétrole/gaz |
WO2019179887A1 (fr) | 2018-03-20 | 2019-09-26 | Hte Gmbh The High Throughput Experimentation Company | Procédé d'analyse de flux de traitement |
DE102020002256A1 (de) | 2020-04-09 | 2021-10-14 | Sartorius Stedim Biotech Gmbh | Prozesssteuerung/-regelung auf Basis einer spektroskopischen Bestimmung unbestimmter Substanzkonzentrationen |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5349188A (en) * | 1990-04-09 | 1994-09-20 | Ashland Oil, Inc. | Near infrared analysis of piano constituents and octane number of hydrocarbons |
WO1996010009A1 (fr) * | 1994-09-28 | 1996-04-04 | Exxon Chemical Patents Inc. | Procede de commande, par l'analyse dans l'infrarouge proche ou moyen, de la conversion d'un ester de polyol |
US5561217A (en) * | 1992-12-23 | 1996-10-01 | Basf Aktiengesellschaft | Preparation of polyether glycols |
EP0801299A1 (fr) * | 1996-04-09 | 1997-10-15 | Bp Chemicals S.N.C. | Commande de processus |
US5712481A (en) * | 1990-04-09 | 1998-01-27 | Ashland Inc | Process and apparatus for analysis of hydrocarbon species by near infrared spectroscopy |
WO1998029787A1 (fr) * | 1996-12-31 | 1998-07-09 | Exxon Chemical Patents Inc. | Controle en direct dans une installation de traitement chimique |
-
1999
- 1999-07-06 FI FI991542A patent/FI991542A/fi unknown
-
2000
- 2000-07-04 WO PCT/FI2000/000610 patent/WO2001002088A1/fr active Search and Examination
- 2000-07-04 AU AU58318/00A patent/AU5831800A/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5349188A (en) * | 1990-04-09 | 1994-09-20 | Ashland Oil, Inc. | Near infrared analysis of piano constituents and octane number of hydrocarbons |
US5712481A (en) * | 1990-04-09 | 1998-01-27 | Ashland Inc | Process and apparatus for analysis of hydrocarbon species by near infrared spectroscopy |
US5561217A (en) * | 1992-12-23 | 1996-10-01 | Basf Aktiengesellschaft | Preparation of polyether glycols |
WO1996010009A1 (fr) * | 1994-09-28 | 1996-04-04 | Exxon Chemical Patents Inc. | Procede de commande, par l'analyse dans l'infrarouge proche ou moyen, de la conversion d'un ester de polyol |
EP0801299A1 (fr) * | 1996-04-09 | 1997-10-15 | Bp Chemicals S.N.C. | Commande de processus |
WO1998029787A1 (fr) * | 1996-12-31 | 1998-07-09 | Exxon Chemical Patents Inc. | Controle en direct dans une installation de traitement chimique |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8174503B2 (en) | 2008-05-17 | 2012-05-08 | David H. Cain | Touch-based authentication of a mobile device through user generated pattern creation |
CN102023140A (zh) * | 2011-01-07 | 2011-04-20 | 安徽中烟工业公司 | Nir技术测定1-2丙二醇含量方法 |
EP2895689A4 (fr) * | 2012-09-14 | 2016-10-05 | Halliburton Energy Services Inc | Systèmes et procédés pour contrôler des processus de séparation pétrole/gaz |
EP2920137A4 (fr) * | 2012-11-13 | 2016-06-15 | Lyondell Chemical Tech Lp | Régulation d'un procédé par spectroscopie raman |
WO2019179887A1 (fr) | 2018-03-20 | 2019-09-26 | Hte Gmbh The High Throughput Experimentation Company | Procédé d'analyse de flux de traitement |
CN111936844A (zh) * | 2018-03-20 | 2020-11-13 | Hte高通量实验公司 | 分析过程工艺料流的方法 |
CN111936844B (zh) * | 2018-03-20 | 2024-04-09 | Hte高通量实验公司 | 分析过程工艺料流的方法 |
US11953433B2 (en) | 2018-03-20 | 2024-04-09 | Hte Gmbh The High Throughput Experimentation Company | Method for analysing process streams |
DE102020002256A1 (de) | 2020-04-09 | 2021-10-14 | Sartorius Stedim Biotech Gmbh | Prozesssteuerung/-regelung auf Basis einer spektroskopischen Bestimmung unbestimmter Substanzkonzentrationen |
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AU5831800A (en) | 2001-01-22 |
FI991542A (fi) | 2001-01-07 |
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